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International audience; Graphene (Gr) is known to be an excellent barrier preventing atoms and molecules to diffuse through it. This is due to the carbon atom arrangement in a two-dimensional (2D) honeycomb structure with a very small lattice parameter thus forming an electron cloud that prevents atoms and molecules crossing. Nonetheless at high an-nealing temperatures, intercalation of atoms through graphene occurs, opening the path for formation of vertical heterojunctions constituted of two-dimensional layers. In this paper, we report on the ability of silicon atoms to penetrate the graphene network, fully epitaxially grown on a Ni(111) surface, even at room temperature. Our scanning tunneling microscopy (STM) experiments show that the presence of defects like vacancies and disloca-tions in the graphene lattice favor the Si atoms intercalation, thus forming two-dimensional, flat and disordered islands below the Gr layer. Ab-initio molecular dynamics calculations confirm that Gr defects are necessary for Si intercalation at room temperature and show that: i) a hypothetical intercalated silicene layer cannot be stable for more than 8 ps and ii) the corresponding Si atoms completely lose their in-plane order resulting in a random planar distribution and form strong covalent bonds with Ni atoms.

In this work, the authors investigated MoO3 films with thickness between 30 nm and 1 μm grown at room temperature by solid phase deposition on polycrystalline Cu substrates. Atomic force microscopy, scanning electron microscopy, and scanning tunneling microscopy revealed the presence of a homogenous MoO3 film with a “grainlike” morphology, while Raman spectroscopy showed an amorphous character of the film. Nanoindentation measurements evidenced a coating hardness and stiffness comparable with the copper substrate ones, while Auger electron spectroscopy, x-ray absorption spectroscopy, and secondary electron spectroscopy displayed a pure MoO3 stoichiometry and a work function ΦMoO3 = 6.5 eV, 1.8 eV higher than that of the Cu substrate. MoO3 films of thickness between 30 and 300 nm evidenced a metallic behavior, whereas for higher thickness, the resistance–temperature curves showed a semiconducting character.In this work, the authors investigated MoO3 films with thickness between 30 nm and 1 μm grown at room temperature by solid phase deposition on polycrystalline Cu substrates. Atomic force microscopy, scanning electron microscopy, and scanning tunneling microscopy revealed the presence of a homogenous MoO3 film with a “grainlike” morphology, while Raman spectroscopy showed an amorphous character of the film. Nanoindentation measurements evidenced a coating hardness and stiffness comparable with the copper substrate ones, while Auger electron spectroscopy, x-ray absorption spectroscopy, and secondary electron spectroscopy displayed a pure MoO3 stoichiometry and a work function ΦMoO3 = 6.5 eV, 1.8 eV higher than that of the Cu substrate. MoO3 films of thickness between 30 and 300 nm evidenced a metallic behavior, whereas for higher thickness, the resistance–temperature curves showed a semiconducting character.

Highly oriented pyrolitic graphite (HOPG) is an inert substrate with a structural honeycomb lattice, well suited for the growth of two-dimensional (2D) silicene layer. It was reported that when Si atoms are deposited on HOPG surface at room temperature, they arrange in two configurations: silicene nanosheets and three dimensional clusters. In this work we demonstrate, by using scanning tunneling microscopy (STM) and Raman spectroscopy, that a third configuration stabilizes in the form of Si 2D nanosheets intercalated below the first top layer of carbon atoms. The Raman spectra reveal a structure located at 538 cm$^{-1}$ which we ascribe to the presence of sp$^2$ Si hybridization. Moreover, the silicon deposition induces several modifications in the graphite D and G Raman modes, which we interpret as an experimental evidence of the intercalation of the silicene nanosheets. The Si atom intercalation at room temperature takes place at the HOPG step edges and it detaches only the outermost graphene layer inducing a strong tensile strain mainly concentrated on the edges of the silicene nanosheets. Theoretical calculations of the structure and energetic viability of the silicene nanosheets, of the strain distribution on the outermost graphene layer and its influence on the Raman resonances support the STM and Raman observations., 18 pages, 9 figures, 2 tables

The microwave conductivity and permittivity of both single-walled and multi-walled carbon nanotube (SWCNT and MWCNT) sponges were measured while compressing the samples. Compression leads to a huge variation of the absorptance, reflectance, and transmittance of the samples. The dependence of the microwave conductivity on the sponge density follows a power-law relation with exponents 1.7 ± 0.1 and 2.0 ± 0.2 for MWCNT and SWCNT sponges, respectively. These exponents can be decreased slightly by the addition of a non-conducting component which partly electrically separates adjacent tubes within the samples. The conductivity of MWCNT sponge was measured in the terahertz range while heating in air from 300 to 513 K and it increased due to an increase of a number of conducting channels in MWCNTs.

Carbon spheres of nanometric dimension are known since the first studies on the synthesis of fullerenes. Their shape originates from the curvature of a carbon sheet similar to fullerenes, but with numerous graphitic rings that regulate the inside structure and the formation of open edges at the surface. This paper focuses on the structural and electronic characterization of carbon spheres obtained from a chemical vapor deposition synthesis process. Two different sets of samples are analyzed in detail, in particular, electron microscopies and Raman spectroscopy help understanding the morphology and the graphitic-sp2 arrangement of the carbon atoms in the architectures. In addition, the iron catalyst used during the reaction process confers the carbon spheres a ferromagnetic response at room temperature. Therefore, both the structural properties of the samples and the active contribution of iron mark the difference in the measured photoresponse as well as in the electrochemical behavior. The X-ray photoelectron spectroscopy study addresses these points by giving information on the composition and the iron chemical state in the assembly. The collected results underline the advantages offered by this nanomaterial for sustainable applications.

Self-assembled hierarchical solid surfaces are very interesting for wetting phenomena, as observed in a variety of natural and artificial surfaces. Here, we report single-walled (SWCNT) and multi-walled carbon nanotube (MWCNT) thin films realized by a simple, rapid, reproducible, and inexpensive filtration process from an aqueous dispersion, that was deposited at room temperature by a dry-transfer printing method on glass. Furthermore, the investigation of carbon nanotube films through scanning electron microscopy (SEM) reveals the multi-scale hierarchical morphology of the self-assembled carbon nanotube random networks. Moreover, contact angle measurements show that hierarchical SWCNT/MWCNT composite surfaces exhibit a higher hydrophobicity (contact angles of up to 137{\deg}) than bare SWCNT (110{\deg}) and MWCNT (97{\deg}) coatings, thereby confirming the enhancement produced by the surface hierarchical morphology., Comment: 7 pages, 5 figures, This article is part of the Thematic Series "Self-assembly of nanostructures and nanomaterials"

A helical hexapeptide was designed to link in a rigid parallel orientation to a gold surface. The peptide sequence of the newly synthesized compound is characterized by the presence of two 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) residues (positions 1 and 4) to promote a bidentate interaction with the gold surface, two L-Ala residues (positions 2 and 5) and two-aminoisobutyric acid (Aib) residues (positions 3 and 6) to favor a high population of the 3(10)-helix conformation. Furthermore, a ferrocenoyl (Fc) probe was inserted at the N-terminus to investigate the electronic conduction properties of the peptide. X-Ray photoelectron spectroscopy and scanning tunneling microscopy techniques were used to characterize the binding of the peptide to the gold surface and the morphology of the peptide layer, respectively. Several electrochemical (cyclic voltammetry, chronoamperometry, square wave voltammetry) techniques were applied to analyze the electrochemical activity of the Fc probe, along with the influence of the peptide 3D-structure and the peptide layer morphology on electron transfer processes.

The extraordinary properties of graphene have spurred huge interest in the experimental realization of a two-dimensional honeycomb lattice of silicon, namely, silicene. However, its synthesis on supporting substrates remains a challenging issue. Recently, strong doubts against the possibility of synthesizing silicene on metallic substrates have been brought forward because of the non-negligible interaction between silicon and metal atoms. To solve the growth problems, we directly deposited silicon on a chemically inert graphite substrate at room temperature. Based on atomic force microscopy, scanning tunneling microscopy, and ab initio molecular dynamics simulations, we reveal the growth of silicon nanosheets where the substrate-silicon interaction is minimized. Scanning tunneling microscopy measurements clearly display the atomically resolved unit cell and the small buckling of the silicene honeycomb structure. Similar to the carbon atoms in graphene, each of the silicon atoms has three nearest and six second nearest neighbors, thus demonstrating its dominant sp

Large nanostructures of silicene have been successfully grown on graphene covered 6H-SiC (0001) substrates. The graphene plays an important role to obtain honeycomb structures of silicon in the sp2 configuration and acts as an ideal template for 2D materials. The scanning tunneling microscopy images showed nanosheets of silicene with a very small buckling among the Si atoms. Our scanning tunneling spectroscopy confirmed the metallic character of the deposited silicene in excellent agreement with band structure calculations that also exhibit the presence of Dirac cones.

Three-dimensional carbon nanotube frameworks favor spinal cord explant rewiring of motor outputs., In modern neuroscience, significant progress in developing structural scaffolds integrated with the brain is provided by the increasing use of nanomaterials. We show that a multiwalled carbon nanotube self-standing framework, consisting of a three-dimensional (3D) mesh of interconnected, conductive, pure carbon nanotubes, can guide the formation of neural webs in vitro where the spontaneous regrowth of neurite bundles is molded into a dense random net. This morphology of the fiber regrowth shaped by the 3D structure supports the successful reconnection of segregated spinal cord segments. We further observed in vivo the adaptability of these 3D devices in a healthy physiological environment. Our study shows that 3D artificial scaffolds may drive local rewiring in vitro and hold great potential for the development of future in vivo interfaces.

Films of multiwall carbon nanotubes (CNTs), arranged on Si/SiO2 substrates, are used as templates for Nb films with thickness in the range 3–50 nm deposited by sputtering. The resulting aggregates show normal state and superconducting properties similar to those observed in networks of superconducting nanowires (SNW) obtained by other methods. Decreasing the Nb thickness, when the normal state resistance becomes larger than the quantum resistance, a superconductor-insulator transition is observed. Moreover, thermally activated phase slips in thicker samples, evolving in quantum phase slips in thinner nanowires, are observed in the superconducting state. The experimental results indicate that the template method based on CNTs is a promising alternative to the much more expensive nanolithography techniques for obtaining SNWs. Even more important, they indicate CNT films as versatile elements in nanostructured electronic devices.

Multidentate binding of two helical hexapeptides to a gold surface was obtained by introducing in the peptide chain a non ribosomial amino acid, i.e. the 4-amino-1,2-dithiolane-4-carboxylic acid (Adt) residue, a C α -tetrasubstituted α-amino acid bearing a heterocyclic side chain characterized by a disulfide group. The two peptides, mainly formed by strongly helicogenic C α -tetrasubstituted α-amino acids, were both functionalized at the N-terminus by a ferrocenoyl (Fc) group, but differ in the number of Adt residues included in the peptide chain: the former (Fc6Adt2) contains two Adt residues at positions 1 and 4, while its analog (Fc6Adt1) contains a single Adt at position 4, since the Adt at position 1 is substituted by an α-amino isobutyric acid (Aib) residue. This peptide design allowed us to explore the different electrochemical properties and morphologies shown by the two peptide layers immobilized on a gold surface by two (Fc6Adt2) or a single (Fc6Adt1) bidentate linker, respectively. The electrochemical activity of the ferrocenoyl probe embedded in the peptide film was characterized by cyclic voltammetry, chronoamperometry and square wave voltammetry, while the binding and the morphology of the peptide layers were studied by X-ray photoelectron spectroscopy (XPS) and ultra high vacuum scanning tunneling microscopy (UHV-STM), respectively. Significant differences were observed in the electron transfer (ET) properties of the two peptides investigated, which emerge from the diverging morphology achieved by the peptide layers on the gold surface. It was found that while a standing-up configuration of the peptide layer, realized by a single bidentate linkage, maximizes the ET efficiency, a lying down configuration (two Adt linkages) allows for precise positioning of Fc in the proximity of a gold surface.

Deoxyribonucleic acid (DNA) was successfully incorporated as a nanolayer between the bottom indium tin oxide (ITO) transparent electrode and the photoabsorbing film in a polymer solar cell. Upon film optimization and analyses with scanning tunneling spectroscopy/currents, we demonstrate that a 1–6 nm thick DNA stratum functions as an effective electron-extracting layer, leading to strong improvements in rectifying behavior (by 2 orders of magnitude with rectifying ratios reached larger than 103) and in photovoltaic parameters like the open-circuit voltage (VOC from 0.39 to 0.73 V) and power conversion efficiencies (PCEs from ∼2 to ∼5%). The results show that DNA is a very ductile nanomaterial for electronic purposes, paving the way for future exploration in photovoltaic devices combining its electron-extracting properties with its functional and self-assembly behavior. Furthermore, solar cell devices were completely processed at room temperature, and DNA was cast from ecofriendly solvents such as water an...

Negative differential resistance (NDR), for which the current is a decreasing function of the voltage, has been observed in the current–voltage curves of several types of structures. We measured tunnelling current and NDR by illuminating large area heterojunction obtained by growing Multi Wall Carbon Nanotubes on the surface of n-doped Silicon substrate. In the absence of light, the current flow is null until a junction threshold of about 2.4 V is reached, beyond which the dark current flows at room temperature with a very low intensity of few nA. When illuminated, a current of tens nA is observed at a drain voltage of about 1.5 V. At higher voltage the current intensity decreases according to a negative resistance of the order of MΩ. In the following we report details of tunneling photodiode realized and negative resistance characteristics.

We have taken advantage of the native surface roughness and the iron content of AISI-316 stainless steel to grow multiwalled carbon nanotubes (MWCNTs) by chemical vapour deposition without the addition of an external catalyst. The structural and electronic properties of the synthesized carbon nanostructures have been investigated by a range of electron microscopy and spectroscopy techniques. The results show the good quality and the high graphitization degree of the synthesized MWCNTs. Through energy-loss spectroscopy we found that the electronic properties of these nanostructures are markedly different from those of highly oriented pyrolytic graphite (HOPG). Notably, a broadening of the π-plasmon peak in the case of MWCNTs is evident. In addition, a photocurrent was measured when MWCNTs were airbrushed onto a silicon substrate. External quantum efficiency (EQE) and photocurrent values were reported both in planar and in top-down geometry of the device. Marked differences in the line shapes and intensities were found for the two configurations, suggesting that two different mechanisms of photocurrent generation and charge collection are in operation. From this comparison, we are able to conclude that the silicon substrate plays an important role in the production of electron–hole pairs.

We report on the multiwall carbon nanotube application as energy conversion material to fabricate thin film solar cells, with nanotubes acting as photogeneration sites as well as charge separators, collectors and carrier transporters. The device consists of a semitransparent thin film of nanotubes coating a n-type crystalline silicon substrate. Under illumination electron-hole (e-h) pairs, generated in the nanotubes and in the silicon substrate underneath, are split and charges are transported through the nanotubes (electrons) and the n-Si (holes). We found that a suitable thickness of the nanotube thin film, high density of Schottky junctions between nanotubes and n-Si and lowest number of nanotube walls are all fundamental parameters to improve the device incident photon to electron conversion efficiency. Multiwall carbon nanotubes have been synthesized by chemical vapour deposition in an ultra high vacuum chamber by evaporating a given amount of iron at room temperature and then exposing the substrate kept at 800 degrees C at acetylene gas. The amount of deposited iron is found to directly affect the nanotube size distribution (inner and outer diameter) and therefore the number of walls of the nanotubes.

We report on the generation of photocurrent in the visible and ultraviolet range from planar devices built from the Ge nanocrystals grown on a heavy n-doped Si(001) substrate covered with 5 nm thick thermally grown SiO2. These Ge nanostructures/SiO2/n(+)-Si devices are shown to generate photocurrent with an Incident-Photon-to-electron Conversion Efficiency (IPCE) spectral range depending on the Ge nanocrystals size. The increase of the IPCE value of our devices in the 350-600 nm range correlates well with the absorbance of Ge.

International audience; Multi wall carbon nanotubes (MWCNTs) were grown on a stainless steel (SS) sheet by chemical vapor deposition without the addition of external metal catalyst. We found that the key for highly efficient growth includes the nanoscale roughness of the SS surface, as shown by scanning tunneling microscopy, that acts as catalyst/template in the nanotube formation. Raman spectroscopy and electron microscopy were used to check the nature and quality of the synthesized nanotubes. We conclude that stainless steel favors a base-growth mechanism. Transmission electron energy loss spectroscopy performed on single metallic particles found inside the nanotubes clarified the atomic nature of the catalytic particles supplied by the steel. Only unoxidized iron was found and no traces of nickel and chromium were detected. In addition, the SS substrate has been used for a second growth process after carefully removing the synthesized CNTs, proving that a continuous production of CNTs from the same substrate is achievable.

The inclusion of carbon nanotubes in polymer matrix has been proposed to enhance the polymer’s physical and electrical properties. In this study, microscopic and spectroscopic techniques are used to investigate the interaction between poly(3-hexylthiophene) (P3HT) and nanotubes and the reciprocal modification of physical properties. The presence of P3HT-covered nanotubes dispersed in the polymer matrix has been observed by atomic force microscopy and transmission electron microscopy. Then, the modification of P3HT optical properties due to nanotube inclusion has been evidenced with spectroscopic techniques like absorption and Raman spectroscopy. The study is completed with detailed nanoscale analysis by scanning probe techniques. The ordered self assembly of polymer adhering on the nanotube is unveiled by showing an example of helical wrapping of P3HT. Scanning tunneling spectroscopy study provides information on the electronic structure of nanotube-polymer assembly, revealing the charge transfer from P3HT to the nanotube.

We show that when a soft polymer like Poly(3-hexyl-thiophene) wraps multiwall nanotubes by coiling around the main axis, a localized deformation of the nanotube structure is observed. High resolution transmission electron microscopy shows that radial compressions of about 4% can take place, and could possibly lead to larger interlayer distance between the nanotube inner walls and reduce the innermost nanotube radius. The mechanical stress due to the polymer presence was confirmed by Raman spectroscopic observation of a gradual upshift of the carbon nanotube G-band when the polymer content in the composites was progressively increased. Vibrational spectroscopy also indicates that charge transfer from the polymer to the nanotubes is responsible for a peak frequency relative downshift for high P3HT-content samples. Continuously acquired transmission electron microscopy images at rising temperature show the MWCNT elastic compression and relaxation due to polymer rearrangement on the nanotube surface.

Controlled synthesis of carbon nanotubes (CNTs) is highly desirable for nanoelectronic applications. To date, metallic catalyst particles have been deemed unavoidable for the nucleation and growth of any kind of CNTs. Ordered arrays of nanotubes have been obtained by controlled deposition of the metallic catalyst particles. However, the presence of metal species mixed with the CNTs represents a shortcoming for most electronic applications, as metal particles are incompatible with silicon semiconductor technology. In the present paper we report on a metal-catalyst-free synthesis of CNTs, obtained through Ge nanoparticles on a Si(001) surface patterned by nanoindentation. By using acetylene as the carbon feed gas in a low-pressure Chemical Vapor Deposition (CVD) system, multi-walled carbon nanotubes (MWNT) have been observed to arise from the smallest Ge islands. The CNTs and the Ge three-dimensional structures have been analysed by SEM, EDX and AFM in order to assess their elemental features and properties. EDX and SEM results allow confirmation of the absence of any metallic contamination on the surface, indicating that the origin of the CNT growth is due to the Ge nanocrystals.

In this work we show that a sizeable enhancement in the photocurrent over the visible and near ultraviolet energy range can be obtained from multi-wall carbon nanotubes when decorated with Cu-nanoparticles. The result has been obtained both from electrochemical and solid state cells measurements. The photoactive metal nanoparticles do not change the intrinsic ability of multi-wall carbon nanotubes to behave as an efficient low dimensional media for generating e–h carriers. This result further confirms that multi wall carbon nanotubes can be used in photovoltaic nano-devices and solar energy conversion applications.

The photocurrent generation of nanometric Ge droplets has been investigated by using electrochemical measurements. Dots have been grown by annealing Ge layers of different nominal thicknesses (ranging from 0.5 to 5 nm) deposited on clean SiO2 surface at room temperature. The photocurrent signals for the largest dots show features, which can be ascribed to the Ge nanocrystals direct electronic transitions. Only in the case of 0.5 nm Ge film a broad and intense feature at 2.4 eV has been observed while the peaks at higher energy result to be dramatically reduced. Since this last sample is characterized by (5±1) nm nanodots size (the smallest among the measured samples) the appearance of this broad band in the photocurrent active spectrum can be ascribed to quantum confinement effect.

Here, we investigate the thickness of single-walled (SWCNT) and multi-walled carbon nanotube (MWCNT) random network films by angle-resolved X-ray photoemission spectroscopy. Furthermore, we estimate the absorption coefficient of carbon nanotube (CNT) films through the Lambert–Beer law, by measuring film optical spectra. Moreover, the knowledge of the absorption coefficient provides an easier, reliable, and faster method of investigation for generic CNT film thickness. In addition, the absorption coefficient leads to the information of the absorption length for SWCNT and MWCNT films, which is a physical quantity of fundamental interest for optoelectronic applications, such as light emitting diodes, photovoltaics, and in general light absorbers.

A hierarchical structure is an assembly with a multi-scale morphology and with a large and accessible surface area. Recent advances in nanomaterial science have made increasingly possible the design of hierarchical surfaces with specific and tunable properties. Here, we report the fractal analysis of hierarchical single-walled carbon nanotube (SWCNT) films realized by a simple, rapid, reproducible and inexpensive filtration process from an aqueous dispersion, then deposited by drytransfer printing method on several substrates, at room temperature. Furthermore, by varying the thickness of carbon nanotube random networks, it is possible tailoring their wettability due to capillary phenomena in the porous films. Moreover, in order to describe the wetting properties of such surfaces, we introduce a two-dimensional extension of the Wenzel-Cassie-Baxter theory. The hierarchical surface roughness of SWCNT coatings coupled with their exceptional and tunable optical and electrical properties provide an ideal hydrophobic composite surface for a new class of optoelectronic and nanofluidic devices.

A significant resonant tunneling effect has been observed under the 2.4 V junction threshold in a large area, carbon nanotube–silicon (CNT–Si) heterojunction obtained by growing a continuous layer of multiwall carbon nanotubes on an n-doped silicon substrate. The multiwall carbon nanostructures were grown by a chemical vapor deposition (CVD) technique on a 60 nm thick, silicon nitride layer, deposited on an n-type Si substrate. The heterojunction characteristics were intensively studied on different substrates, resulting in high photoresponsivity with a large reverse photocurrent plateau. In this paper, we report on the photoresponsivity characteristics of the device, the heterojunction threshold and the tunnel-like effect observed as a function of applied voltage and excitation wavelength. The experiments are performed in the near-ultraviolet to near-infrared wavelength range. The high conversion efficiency of light radiation into photoelectrons observed with the presented layout allows the device to be used as a large area photodetector with very low, intrinsic dark current and noise.

Transmission electron microscopy (TEM) and electron energy loss near-edge structure (EELNES) revealed the presence of mostly non-oxidised silicon tubular structures among the reaction products synthesized by gas phase condensation technique. Scanning tunneling microscopy (STM) showed a hexagonal atomic arrangement for straight ones. The presence of Y-, T-branched and coiled tubular structure, like in carbon nanotubes, suggests a partially sp2 hybridization. Reflection energy loss measurements confirmed the presence of thin tubular structures and gave hint of sp3 bonds.

We report on a new photodetector fabricated using carbon nanostructures grown on a silicon substrate. This device exhibits low noise, a good conversion efficiency of photons into electrical current and a good signal linearity in a wide range of radiation wavelengths ranging from ultraviolet to infrared at room temperature. The maximum quantum efficiency of 37% at 880 nm has been measured without signal amplification. Such innovative devices can be easily produced on large scales by Chemical Vapour Deposition (CVD) through a relatively inexpensive chemical process, which allows large sensitive areas from a few mm2 up to hundreds of cm2 to be covered.

Ge nanodots, produced by solid phase crystallization of amorphous Ge layers deposited at room temperature on SiO 2 thermally grown on a Si(100) surface, generate a photocurrent in the visible and ultraviolet range. The photocurrent signal was detected by measuring the current flowing through the sample under irradiation either in planar or in up-down geometry. In both cases the quantum efficiency of the bare SiO 2 /Si(100) substrate was dramatically enhanced up to a factor of 10 3 . Current–voltage curves were acquired in the latter geometry, evidencing an increase in the short circuit current induced by the Ge nanodots presence.

Zirconia-based Ormosil planar waveguides with different ZrO 2 contents were produced by a low temperature sol–gel process and subsequent spin coating on microscope glass slides. Propagation losses as low as 0.5 dB/cm or less were found at 488 nm for films with low ZrO 2 content; in contrast, worse waveguide quality was observed with increasing ZrO 2 doping level. A morphological investigation by atomic force microscopy confirmed such result, giving evidence of an increase of surface roughness with ZrO 2 percentage. The feasibility of organic dye doping of the films for active waveguides was also demonstrated by incorporation of DODCI saturable absorber: fluorescence spectra were registered both in bulk and guided-wave configuration.

Photovoltaic devices based on single wall carbon nanotubes (SWCNTs) and n-silicon multiple heterojunctions have been fabricated by a SWCNT film transferring process. We report on the ability of the carbon nanotubes to extend the Si spectral range towards the near ultraviolet (UV) and the near infrared regions. Semiconducting and about metallic SWCNT networks have been studied as a function of the film sheet resistance, Rsh. Optical absorbance and Raman spectroscopy have been used to assign nanotube chirality and electronic character. This gave us hints of evidence of the participation of the metal nanotubes in the photocurrent generation. Moreover, we provide evidence that the external quantum efficiency spectral range can be modulated as a function of the SWCNT network sheet resistance in a hybrid SWCNT/Si solar cell. This result will be very useful to further design/optimize devices with improved performance in spectral regions generally not covered by conventional Si p–n devices.

The properties of carbon nanotubes (CNTs), the new allotropic status of carbon discovered in 1991, have been widely investigated in all possible application field. This new material in fact can be easily obtained chemically by CVD (Chemical Vapour Deposition) as a layer of nanotubes growth on a wide variety of materials. When growth on a silicon surface, CNTs create a semiconductor heterojunction with peculiar photoresponsivity properties. We studied this heterojunction with the purpose to realize a large photocathode with high quantum efficiency in a large wavelength range from UV to IR. Results obtained up to day allowed us to build a new kind of photodetector very cheap, stable and easy to manage. Recently this new device has been proposed as one of candidates for the beam monitor system of SuperB.

An angle resolved X-ray photoemission study of carbon nanotube/silicon hybrid photovoltaic (PV) cells is reported, providing a direct probe of a chemically inhomogeneous, Si–O buried interface between the carbon nanotube (CNT) networked layer and the n-type Si substrate. By changing the photoelectron takeoff angle of the analyzer, a nondestructive in-depth profiling of a CNT/SiOx/SiO2/Si complex interface is achieved. Data are interpreted on the basis of an extensive modeling of the photoemission process from layered structures, which fully accounts for the depth distribution function of the photoemitted electrons. As X-ray photoemission spectroscopy provides direct access to the buried interface, the aging and the effects of chemical etching on the buried interface have been highlighted. This allowed us to show how the thickness and the composition of the buried interface can be related to the efficiency of the PV cell. The results clearly indicate that while SiO2 is related to an increase of the efficie...

Straight and coiled single-wall carbon nanotubes (SWCNTs) synthesized by laser vaporization were dispersed on highly oriented pyrolitic graphite. Their morphology and electrical properties were investigated by scanning tunneling microscopy (STM). STM images revealed that the SWCNTs (either straight or coiled) often self-organize into bundles of two or more tubes and are rarely found alone. The conductance measured along a periodically coiled CNT was found to increase at locations where the CNT is squeezed, while it decreases significantly in unsqueezed regions characterized by an unperturbed hexagonal network. This provides experimental evidence of significant conductance modulation along a one-dimensional system on the nanometer scale.

The relaxation dynamics of unaligned multi-walled carbon nanotubes decorated with metallic nanoparticles have been studied by using transient optical measurements. The fast dynamics due to the short-lived free-charge carriers excited by the pump are not affected by the presence of nanoparticles. Conversely, a second long dynamics, absent in bare carbon nanotubes, appears only in the decorated samples. A combination of experiment and theory allows us to ascribe this long dynamics to relaxation channels involving electronic states localized at the tube-nanoparticle interface.

International audience; A simple method to decorate multiwalled carbon nanotubes (MWCNTs) with Au, Ag and Cu nanoparticles is illustrated. The method consists in directly depositing the selected metals by thermal evaporation on the carbon nanotubes. Comparative measurements carried out on samples that differ in the quantity and type of the deposited metal, reveal that isolated discrete particles form on the nanotube outer wall for all three metals. The CNT-based composites have been investigated by scanning and transmission electron microscopy to determine the size, shape and distribution of the nanoparticles. The results indicate that the quantity of evaporated metal only affects the nanoparticle size and not the average particle density. Particle composition was determined by X-ray photoelectron spectroscopy study. The results are discussed in terms of metal nanoparticle-tube interactions, an important issue for the fundamental and practical applications of similar MWCNT based composites.

International audience; Multiwalled carbon nanotubes synthesized directly on austenitic stainless steel result in being filled with pure iron nanoparticles. X-ray diffraction shows that the nanoparticles are either in the γ- or α-phase, although iron in the original alloy is in γ-phase because of the presence of nickel. This phase transformation is due to the selective extraction of iron, performed by carbon nanotubes during their growth. A high coercivity of iron-filled carbon nanotubes is measured although the starting steel is paramagnetic. The presence of the α-phase, the magnetic anisotropy and the single domain character of the Fe nanoparticles explain their magnetic behavior.

The realization of a Silicon Carbon Nanotube heterojuntion opens the door to a new generation of photodetectors (Si-CNT detector) based on the coupling between this two materials. In particular the growth of Multiwall Carbon Nanotubes on the surface of a n-doped silicon substrate results on a Schottky diode junction with precise rectifying characteristics. The obtained device presents a low dark current, high efficiency in the photoresponsivity, high linearity and a wide stability range. The junction barrier is about 3.5 V in reverse polarity with a breakdown limit at more than 100 V. The spectral behavior reflects the silicon spectral range with a maximum at about 880 nm.

We report on the characteristics of a new class of Si-based nanotubes and spherical nanoparticles synthesized by the dc-arc plasma method in a mixture of argon and hydrogen. These two nanostructures share common properties: they are hollow and possess very thin, highly polycrystalline and mainly oxidized walls. In particular, we get several hints indicating that their walls could constitute only one single Si oxidized layer. Moreover, we find that only the less oxidized nanotubes exhibit locally atomic ordered, snakeskin-like areas which possess a hexagonal arrangement which can be interpreted either as an sp(2) or sp(3) hybridized Si or Si-H layer. Their ability to not react with oxygen seems to suggest the presence of sp(2) configuration or the formation of silicon-hydrogen bonding.

A new class of radiation detectors based on carbon nanostructures as the active photosensitive element has been recently developed. In this scenario the optimization of the device, both in dark and on light irradiation, is a crucial point. Here, we report on electrical measurements performed in dark conditions on carbon nanofibers and nanotubes deposited on silicon substrates. Our experimental results were interpreted in terms of a multistep tunneling process occurring at the carbon nanostructures/silicon interface.

We report on a significant photocurrent generation from a planar device obtained by coating a bare n doped silicon substrate with a random network of multiwall carbon nanotubes (MWCNTs). This MWCNT/n-Si hybrid device exhibits an incident photon to current efficiency reaching up to 34% at 670 nm. We also show that MWCNTs covering a quartz substrate still exhibit photocurrent, though well below than that of the MWCNTs coating the silicon substrate. These results suggest that MWCNTs are able to generate photocurrent and that the silicon substrate plays a fundamental role in our planar device. The former effect is particularly interesting because MWCNTs are generally known to mimic the electronic properties of graphite, which does not present any photocurrent generation. On the basis of theoretical calculations revealing a weak metallic character for MWCNTs, we suggest that both metallic and semiconducting nanotubes are able to generate e-h pairs upon illumination. This can be ascribed to the presence of van Hove singularities in the density of states of each single wall carbon nanotube constituting the MWCNT and to the low density of electrons at the Fermi level. Finally, we suggest that though both MWCNTs and Si substrate are involved in the photocurrent generation process, MWCNT film mainly acts as a semitransparent electrode in our silicon-based device.

We have investigated the morphology, chemical bonds and electronic states of CVD carbon grown on silicon (111) substrates by means of scanning electron microscopy (SEM), Auger electron spectroscopy (AES), ultraviolet photoemission spectroscopy (UPS) and optical reflectivity. Both AES and UPS techniques show variations in the observed spectra if referred to samples at different stages of growth. The optical reflectivity technique has also been used in order to study the diamond-substrate interface and to quantify the film thickness.

Among the carbon allotropes newly discovered during the last few decades, carbon nanotubes (CNTs) have attracted enormous attention due to their structural and electronic properties with strong one dimensional character. The physical and chemical features of such systems are intrinsically rich and complex, and can only be probed by using multiple experimental and theoretical techniques. In this feature, we focus on the structural and electronic properties of CNTs that can be accessed by using transmission electron energy loss spectroscopies. The latter are complementary to optical and X-ray absorption techniques, yet allow to obtain the electronic structure with nanoscale spatial resolution. An improved understanding of the structure-electronic properties relationship of these unique 1D systems would represent a fundamental advance, and holds the promise of using CNTs in future applications.

We report photocurrent generation in entangled networks of multiwall-carbon nanotubes (MWCNTs) grown on TiN/Si substrates by an all-laser process. By integrating these MWCNTs into planar devices, we demonstrate that they generate photocurrent over all the visible and near-ultraviolet range, with maximum efficiency around 420 nm. Photocurrent is obtained even at zero applied voltage, pointing to a true photovoltaic (PV) effect. The extracted photocurrent as a function of applied voltage exhibits nonlinear behavior for voltages ≥2 V, suggesting that the devices do not behave as pure photoresistances. Other mechanisms (e.g., Schottky barriers imbalance) are invoked to describe current flow in these PV devices.

Mixtures of regioregular poly(3-hexyl-thiophene) (rrP3HT) and multiwall carbon nanotubes have been investigated by scanning tunneling microscopy in ultrahigh vacuum. Carbon nanotubes covered by rrP3HT have been imaged and analyzed, providing a clear evidence that this polymer self-assembles on the nanotube surface following geometrical constraints and adapting its equilibrium chain-to-chain distance. Largely spaced covered nanotubes have been analyzed to investigate the role played by nanotube chirality in the polymer wrapping, evidencing strong rrP3HT interactions along well defined directions.

We compare the local order in single-wall carbon nanotubes (SWCNTs) and highly oriented pyrolitic graphite (HOPG) by means of nanoscale transmission extended energy loss fine structure (EXELFS) measurements above the carbon K edge. The HOPG EXELFS spectra and their Fourier transform were compared to their synchrotron extended X-ray absorption fine structure (EXAFS) counterpart and discussed within a multiple scattering framework. By comparing the experimental EXELFS data to spectra calculated using a theoretical model based on a single scattering approach, we showed the fundamental importance of considering multiple paths (involving up to eight body scattering) to reproduce the fine details of EXELFS features. Simulating EXELFS spectra of SWCNTs by our theoretical model is shown to represent a measure of their chiralities. Finally, the shrinkage of the nearest-neighbor distance in the Fourier transform observed for SWCNTs (absent in graphite) is interpreted within a simple model invoking anharmonic effects.

We give a quantitative estimate of the screened on-site Coulomb repulsion U in carbon nanotubes and graphite. This is obtained by measuring the Auger spectrum of these materials and performing a theoretical study based on the Green's function method proposed by Cini[Solid. St. Comm. 24, 681 (1977)]. The experimental lineshape is very well reproduced by the theory, where only one fit parameter is employed. This allows to extract the value of the screened on-site repulsion between 2p states, which results U = 4.6 eV for nanotubes and U = 2.1 eV for graphite.

The ordering properties of tetraphenylporphyrin molecules sublimated on a highly oriented pyrolitic graphite surface have been investigated. The morphological information obtained by scanning tunneling microscopy has been linked with the optical spectra by reflectance anisotropy spectroscopy. Measurements were performed in situ as a function of the nominal coverage.

A comparative study of the structure of free-standing parallel bundles of single-wall carbon nanotubes (SWCNTs), multiwalled carbon nanotubes (MWCNTs), and highly oriented pyrolytic graphite (HOPG) was achieved by means of transmission electron microscopy and electron energy loss spectroscopy analyses. In particular, the carbon K (1s) extended fine structure of SWCNTs is found to be characterized by an apparent contraction of the nearest neighbors distance. This contraction is interpreted here to originate from an asymmetric pair distribution function, mostly due to the high out-of-plane vibrational motion of the C atoms, as for the case of chemisorbed atoms on clean surfaces. In contrast, the MWCNTs did not exhibit any signature of such an anharmonic effect because of their more rigid structure. This indicates that the SWCNTs pair potential is significantly broader and its effect is much weaker than that experienced by the same C-C pair embedded in a multiwall nanotube.

Photocurrent generation of nanometric Ge dots has been investigated by using electrochemical measurements. Photocurrent features have been ascribed, for large Ge dots, to Ge bulk direct electronic transitions at L and X points as evidenced by their close correspondence with the optical absorption coefficient. A blueshift of the photocurrent features has been detected by reducing the Ge dot size. These changes have been interpreted as due to quantum confinement effect. This result suggests that Ge dots could be applied in photovoltaic nanodevices and quantum dot based lasers.